Classifications

• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
  • A01N59/16—Heavy metals; Compounds thereof
  • A01N59/20—Copper
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
  • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
  • A01N25/10—Macromolecular compounds
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
  • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
  • A01N33/02—Amines; Quaternary ammonium compounds
  • A01N33/12—Quaternary ammonium compounds
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
  • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof

Definitions

• the present invention relates to the field of materials, preferably surfaces having biocidal, bactericidal and / or bacteriostatic properties.
• the present application relates to a process for the preparation of a biocidal, bactericidal and / or bacteriostatic material capable of delivering singlet oxygen as a biocidal, bactericidal agent and / or comprising a molecule exhibiting bacteriostatic activity.
• Cellulosic supports such as textiles and fabrics represent an environment conducive to the growth of microorganisms (including bacteria, fungi and viruses).
• photo-sensitizers in particular of the porphyrin type, have the particularity, in the presence of visible light, of releasing singlet oxygen, a reactive species which damages or destroys cells and microorganisms.
• singlet oxygen if the singlet oxygen has not reacted with a cell or a microorganism, it returns to its ground state harmlessly.
• the incorporation of photo-sensitizers into and / or on the surface of a cellulosic support offers the possibility of obtaining surfaces having long-term photo-bactericidal properties and producing no toxic secondary product for its environment. However, this requires chemically grafting, via a covalent bond, the photo-sensitizer onto the support to avoid any phenomenon of release of the active compound.
• porphyrins as a bactericidal agent requires severe conditions (high temperature, use of carcinogens, mutagens and / or reprotoxics). Furthermore, when the support of the material is composed of fibers, such as cellulosic fibers or synthetic fibers, grafting porphyrins requires working on isolated fibers before they are shaped, making the process complex.
• BERTHELOT et al. (W02018 / 069508) have developed a process consisting in modifying a porphyrin so as to introduce an arylazide function which can react with the surface of a support via an insertion reaction.
• the UV irradiation of the modified support makes it possible to obtain a material having antibacterial properties.
• the method of BERTHELOT et al. requires pre-functionalization steps of the photo-sensitizer before it is grafted onto a support.
• the material does not exhibit biocidal activities in the dark, which limits the potential applications of this material.
• At least one of the monomers chosen from: i. a monomer C comprising a quaternary amine and a radical polymerizable function; and or
• a monomer D comprising copper and a radical polymerizable function.
• the invention therefore relates to a process for the preparation of a biocidal, bactericidal and / or bacteriostatic material, said process comprising:
• a monomer C comprising a quaternary amine and a radical polymerizable function
• a monomer D comprising copper and a radical-polymerizable function
• UV irradiation of the polymerization of the precursor solution of polymer impregnated in the support according to step (b), said UV irradiation being carried out at an absorption wavelength less than the wavelength maximum maximum absorption of monomer A;
• the monomer A is a protoporphyrin, preferably the dimethyl ester protoporphyrin or the disodium salt of the protoporphyrin.
• the monomer C is chosen from (meth) acrylates comprising a quaternary amine; preferably is (2- (acryloyloxy) ethyl) trimethylammonium chloride.
• the monomer D is chosen from (meth) acrylates comprising copper or di (meth) acrylates comprising copper; preferably copper acrylate or copper dimethacrylate.
• the photoinitiator has a maximum absorption wavelength of from 350 nm to 400 nm; preferably 360 to 380 nm; more preferably around 365 nm.
• the polymer precursor solution further comprises a solvent, preferably chosen from polar solvents, more preferably a water / ethanol mixture or dimethylsulfoxide (DMSO).
• a solvent preferably chosen from polar solvents, more preferably a water / ethanol mixture or dimethylsulfoxide (DMSO).
• the present invention also relates to a precursor solution of a biocidal, bactericidal and / or bacteriostatic polymer, said solution comprising the mixture of: a. at least one monomer A having a porphyrin group and at least one radical polymerizable function, b. at least one radical polymerizable monomer B, c. a photo-initiator, d. at least one of the monomers chosen from: i. a monomer C comprising a quaternary amine and a radical polymerizable function; and / or ii. a monomer D comprising copper and a radical polymerizable function, e. optionally, a solvent.
• the present invention also relates to a biocidal, bactericidal and / or bacteriostatic material comprising a support impregnated with a polymer matrix resulting from the radical polymerization of a precursor polymer solution as described above.
• the present invention also relates to the use of the polymer precursor solution as described above or of the biocidal, bactericidal and / or bacteriostatic of the invention, for the preparation of protective clothing or protective coatings.
• the polymer precursor solution of the invention or the biocidal, bactericidal and / or bacteriostatic material of the invention is useful for sterilization and / or decontamination of a surface.
• Bactericide refers to any compound or material intended to kill bacteria.
• Bocteriostatic refers to any compound or material capable of inhibiting the multiplication and / or production of bacteria without killing them.
• Biocide refers to any compound or material used to kill, destroy, deteriorate, render harmless, prevent action or combat organisms; preferably single-celled organisms including, for example, eukaryotic or prokaryotic cells.
• the organisms are chosen from bacteria, fungi, viruses and / or yeasts.
• From X to Y refers to the range of values between X and Y, the limits X and Y being included in said range.
• Polymerizable radical function relates to any organic chemical function capable of being involved in a radical polymerization reaction, that is to say capable of providing after activation, at least one active radical species capable to react with the radical polymerizable function of another monomer unit so as to form a single bond, preferably of carbon-carbon or carbon- type oxygen.
• the radical-polymerizable function is chosen from the acrylate, methacrylate, styrenic, vinyl and acrylamide functions.
• UV irradiation relates to any action of light having a wavelength included in the ultraviolet range on a chemical compound or a material.
• “Wavelength” represents the spatial periodicity of the oscillations of an electromagnetic wave, that is to say the distance between two maximum oscillations of an electromagnetic wave.
• the wavelength is expressed in meters (m).
• the expression “absorption wavelength” designates the wavelength of the light after it has passed through a compound or a material.
• max designates the wavelength for which the absorbance is maximum.
• “Monomer” relates, within the meaning of the present invention, to any organic compound having at least one radical polymerizable function, that is to say which is capable of being engaged in a radical polymerization reaction.
• the term “monomer” designates any organic chemical compound comprising one or more functions chosen from acrylates, methacrylates, styrenics, vinyls, and acrylamides, preferably chosen from acrylates and methacrylates.
• the term “monomer” includes the macromolecular chains, preferably obtained by polymerization, comprising at least one radical polymerizable function.
• Photoinitiator relates to any compound capable, under the action of light, of initiating radical polymerization.
• Polymer relates to a material comprising or consisting of one or more macromolecular chains.
• the term “polymer” denotes, in the present invention, the product of a radical polymerization.
• the term “polymer” designates in the present invention the product of a polymerization carried out from monomers as defined above, that is to say from organic compounds having at least one radical polymerizable function including, for example, acrylates, methacrylates, styrenics, vinyls and acrylamides.
• Polymerization relates to any organic reaction leading to the formation of one or more macromolecular chains, each comprising the repetition of a chemical unit.
• the term “polymerization” designates a radical polymerization reaction characterized by a priming step, a propagation step and a termination step, well known to those skilled in the art. According to one embodiment, the term “polymerization” designates a radical polymerization reaction from monomers as defined above.
• Porphyrin designates any compound comprising a heterocyclic macrocycle consisting of four pyrrole subunits joined on their alpha carbons by four methine bridges.
• the term “porphyrin” also includes derivatives of porphyrin, that is to say porphyrins substituted by one or more chemical functions, for example by linear or branched alkyls, alkenes, alkynes, heteroalkyls, carboxylic acids, esters, ketones, aldehydes, hydroxyls, amines and radical polymerizable functions as defined above.
• the term “porphyrin” includes protoporphyrins, their derivatives including protoporphyrins substituted by one or more chemical functions, and their salts such as, for example, the disodium salt of protoporphyrin. According to one embodiment, the term “porphyrin” includes the dimethyl ester protoporphyrin.
• Polymer precursor solution relates to any liquid mixture resulting, after polymerization, in obtaining a polymer as defined above.
• Polar solvent relates to any solvent having a non-zero dipole moment.
• the present invention relates to a process for the preparation of a material, preferably a material having biocidal, bactericidal and / or bacteriostatic properties.
• the material of the invention has a bactericidal and biocidal activity against bacterial spores and / or a bacteriostatic activity.
• the material of the invention generates singlet oxygen as a bactericidal agent.
• the material comprises or consists of a support and a coating.
• the method of the invention is a method of polymerization and / or grafting onto a support, of a coating comprising or consisting of a polymer.
• the method of the invention is a method of polymerization and / or impregnation on a support, of a coating comprising or consisting of a polymer.
• the coating has a biocidal activity against bacterial spores and / or a bacteriostatic activity.
• the coating generates singlet oxygen as a bactericidal agent.
• the method of the invention comprises at least one step of preparing a precursor solution of polymer (also called “ink”) (step noted (a)).
• the polymer precursor solution comprises or consists of the mixture of at least one monomer, preferably at least one monomer A having a porphyrin group and at least one function which can be polymerized by the radical route, with a photo - initiator.
• the polymer precursor solution comprises or consists of the mixture of at least one monomer A having a porphyrin group and at least one radical polymerizable function, at least one monomer B radical polymerizable, and a photo - initiator.
• the monomer A is a porphyrin or one of its derivatives.
• the term "porphyrin derivative” means any substituted porphyrin, preferably any porphyrin substituted on at least one of its pyrrole rings and / or on at least one of its methine bridges.
• the monomer A is a porphyrin substituted with at least one group chosen from alkyl, heteroalkyl, alkene, aryl, heteroaryl, cycloalkyl and any radical polymerizable function such as, for example, acrylate, methacrylate, vinyl, or acrylamide; said group possibly being substituted by at least one substituent chosen from alkyl, heteroalkyl, alkene, aryl, heteroaryl, cycloalkyl, carboxylic acid, hydroxyl, amine and ketone.
• the monomer A is a porphyrin substituted by at least one group chosen from alkyl, heteroalkyl, alkene, aryl, heteroaryl, cycloalkyl and any radical polymerizable function such as, for example, acrylate, methacrylate, styrenic, vinyl, or acrylamide; said group possibly being substituted by at least one substituent chosen from alkyl, heteroalkyl, alkene, aryl, heteroaryl, cycloalkyl, carboxylic acid, hydroxyl, amine and ketone.
• the monomer A is a porphyrin substituted by at least one alkyl group, an alkene group and an alkyl group substituted by a carboxylic function.
• the monomer A is a protoporphyrin or one of its salts and / or derivatives, preferably a protoporphyrin IX, more preferably the monomer A is the dimethyl ester protoporphyrin.
• the term “protoporphyrin salt” means any protoporphyrin for which at least one of the protons of the carboxylic functions of protoporphyrin has been replaced by an alkaline cation such as for example by a lithium ion, (Li +), sodium (Na +), potassium (K +), rubidium (Rb +), Cesium (Cs +) or Francium (Fr +).
• the monomer A is a protoporphyrin salt, preferably the protoporphyrin disodium salt.
• the monomer B is chosen from any organic compound (including compounds of low molar masses and compounds of high molar masses such as macromolecular chains) having at least one function which can be polymerized by radical means, preferably any organic compound having at least one function chosen from acrylates, methacrylates, styrenics, vinyls and acrylamides, preferably chosen from acrylates and methacrylates, more preferably said monomer B is 2- (dimethylamino) ethylacrylate.
• the monomer B is a macromolecular chain having at least one radical polymerizable function; preferably monomer B is a macromolecular chain obtained by any polymerization technique known to a person skilled in the art, and comprising at least one radical polymerizable function; more preferably, said monomer B is a poly (ethylene glycol) chain comprising at least one acrylate or methacrylate function, more preferably said monomer B is poly (ethylene glycol) diacrylate (PEGDA).
• PEGDA poly (ethylene glycol) diacrylate
• the photoinitiator is chosen from those known to those skilled in the art.
• the photoinitiator is a radical photoinitiator, preferably chosen from phosphine oxides, acetophenone and its derivatives, benzoin ethers, benzophenone and its derivatives, thioxanthone and its derivatives, benzyl and its derivatives, more preferably the photoinitiator is dipheny 1 (2,4,6-trimethylbenzoyl) phosphine oxide.
• the photoinitiator has a maximum absorption wavelength less than the maximum absorption wavelength of monomer A, preferably said photoinitiator has a wavelength absorption from 350 nm to 400 nm; preferably 360 to 380 nm; more preferably around 365 nm.
• the precursor polymer solution further comprises at least one compound having a biocidal, bactericidal and / or bacteriostatic activity, partial or total, in the dark.
• the compound having a biocidal, bactericidal and / or bacteriostatic activity, partial or total, in the dark is one of the monomers chosen from: a. a monomer C comprising a quaternary amine and a radical polymerizable function as defined above; and / or b. a monomer D comprising copper and a radical polymerizable function as defined above.
• the monomer C is chosen from (meth) acrylates comprising a quaternary amine, preferably is chosen from (acryloyloxyalkyl) alkylammmonium, more preferably is (2- (acryloyloxy) ethyl) trimethylammonium.
• the monomer C comprises a halogenated counterion, preferably a chloride counterion.
• the monomer D is chosen from (meth) acrylates comprising copper, preferably is a copper acrylate or a dimethacrylate comprising copper, more preferably is copper dimethacrylate (ie ie a complex formed by a copper ion (Cu 2+ ) complexed with two methacrylate molecules).
• the precursor polymer solution consists of or comprises: a. at least one monomer A having a porphyrin group and at least one radical polymerizable function, b. at least one monomer B which can be polymerized by the radical route, vs. a photo-initiator,
• a monomer C comprising a quaternary amine and a radical polymerizable function
• a monomer D comprising copper and a radical polymerizable function.
• the polymer precursor solution comprises the monomer A in a range of more than 0% to 10%, preferably more than 0% to 9%, more than 0% to 8%, more than 0% to 7%, more than 0% to 6%, more than 0% to 5%, more than 0% to 4%, more than 0% to 3%, more than 0% at 2%, or more than 0% to 1%, by weight relative to the total weight of the polymer precursor solution.
• the polymer precursor solution comprises approximately 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10% of monomer A, the percentages being expressed by weight relative to the total weight of the polymer precursor solution.
• the precursor polymer solution comprises approximately 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0, 8%, 0.9% or 1% of monomer A, the percentages being expressed by weight relative to the total weight of the polymer precursor solution.
• the monomer A when the precursor polymer solution comprises a solvent, the monomer A represents a mass amount of more than 0% to 10%, preferably more than 0% to 1%, by weight relative to the total weight of the polymer precursor solution.
• the polymer precursor solution comprises a solvent
• the monomer A represents a mass quantity approximately equal to 0.1% by weight relative to the total weight of the polymer precursor solution.
• the monomer A when the polymer precursor solution does not comprise a solvent, the monomer A represents a mass amount of more than 0% to 10%, preferably more than 0% to 1%, by weight relative to the total weight of the polymer precursor solution. According to one embodiment, when the polymer precursor solution does not comprise a solvent, the monomer A represents a mass quantity approximately equal to 0.3% by weight relative to the total weight of the polymer precursor solution.
• the precursor polymer solution comprises monomer B in a range of more than 0% to 50%, preferably from 1% to 40%, from 1% to 30%, from 1% to 20%, or from 1% to 10% by weight relative to the total weight of the solution polymer precursor.
• the precursor polymer solution comprises approximately 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13 %, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46% , 47%, 48%, 49% or 50% of monomer B, the percentages being expressed by weight relative to the total weight of the polymer precursor solution.
• the monomer B when the polymer precursor solution does not comprise a solvent, the monomer B represents a mass amount of more than 0% to 50%, by weight relative to the total weight of the polymer precursor solution. According to one embodiment, when the polymer precursor solution comprises a solvent, the monomer B represents a mass amount of more than 0% to 30%, by weight relative to the total weight of the polymer precursor solution. According to one embodiment, when the polymer precursor solution does not comprise a solvent, the monomer B represents a mass quantity approximately equal to 23% or 41% by weight relative to the total weight of the polymer precursor solution. According to one embodiment, when the polymer precursor solution comprises a solvent, the monomer B represents a mass quantity approximately equal to 10% or 20% by weight relative to the total weight of the polymer precursor solution.
• the polymer precursor solution comprises the photoinitiator in a range of more than 0% to 30%, preferably from 1% to 25%, from 1% to 20%, from 1% 15%, 1% to 10%, or 1% to 5% by weight relative to the total weight of the polymer precursor solution.
• the precursor polymer solution comprises the photoinitiator in a mass quantity approximately equal to 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26% , 27%, 28%, 29% or 30% by weight relative to the total weight of the polymer precursor solution.
• the photoinitiator represents a mass amount of more than 0% to 30%, preferably from 1% to 20%, by weight relative to the weight total of the polymer precursor solution.
• the photoinitiator represents a mass quantity approximately equal to 13% or 17% by weight relative to the total weight of the polymer precursor solution.
• the photoinitiator when the polymer precursor solution comprises a solvent, the photoinitiator represents a mass amount of more than 0% to 20%, of preferably from 1% to 10%, by weight relative to the total weight of the polymer precursor solution. According to one embodiment, when the polymer precursor solution comprises a solvent, the photoinitiator represents a mass quantity approximately equal to 6% or 7% by weight relative to the total weight of the polymer precursor solution.
• the mass ratio of the monomer C to the monomer D varies from more than 0 to 10, preferably from 1 to 6, more preferably said mass ratio is approximately equal to 4 or 5.
• the mass ratio of the monomer C on the monomer D is approximately equal to 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.
• the polymer precursor solution comprises the monomer C in a range of more than 0% to 60%, preferably from 1% to 50%, from 1% to 40%, from 1% to 30%, from 1% to 20%, or from 1% to 10%, the percentages being expressed by weight relative to the total weight of the polymer precursor solution.
• the precursor polymer solution comprises approximately 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13 %, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46% , 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59% or 60% of monomer C, by weight relative to the total weight of the polymer precursor solution.
• the monomer C when the polymer precursor solution does not comprise a solvent, the monomer C represents a mass amount of more than 0% to 50%, by weight relative to the total weight of the polymer precursor solution. According to one embodiment, when the polymer precursor solution does not comprise a solvent, the monomer C represents a mass quantity approximately equal to 30%, 38%, 40% or 50% by weight relative to the total weight of the precursor solution of polymer. According to one embodiment, when the polymer precursor solution comprises a solvent, the monomer C represents a mass amount of more than 0% to 30%, by weight relative to the total weight of the polymer precursor solution.
• the monomer C when the precursor polymer solution comprises a solvent, the monomer C represents a mass amount approximately equal to 15%, 17%, 19% or 21% by weight relative to the total weight of the precursor polymer solution .
• the polymer precursor solution comprises the monomer D in a range of more than 0% to 20%, preferably from 1% to 15%, from 1% to 10%, or from 1% at 5% by weight relative to the total weight of the polymer precursor solution.
• the precursor polymer solution comprises approximately 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13 %, 14%, 15%, 16%, 17%, 18%, 19%, or 20%, of monomer D by weight relative to the total weight of the polymer precursor solution.
• the monomer D represents a mass amount of more than 0% to 20%, preferably from 1% to 15%, more preferably from 5% to 12 % by weight relative to the total weight of the polymer precursor solution.
• the monomer D when the polymer precursor solution does not comprise a solvent, the monomer D represents a mass quantity approximately equal to 8% or 10% by weight relative to the total weight of the polymer precursor solution. According to one embodiment, when the precursor polymer solution comprises a solvent, the monomer D represents a mass amount of more than 0% to 10%, preferably from 1% to 8%, by weight relative to the total weight of the polymer precursor solution. According to one embodiment, when the polymer precursor solution comprises a solvent, the monomer D represents a mass quantity approximately equal to 4% by weight relative to the total weight of the polymer precursor solution.
• the precursor polymer solution consists of or comprises:
• a polar solvent preferably dimethyl sulfoxide (DMSO)
• DMSO dimethyl sulfoxide
• the precursor polymer solution consists of or comprises:
• a polar solvent preferably dimethyl sulfoxide (DMSO)
• DMSO dimethyl sulfoxide
• the precursor polymer solution consists of or comprises:
• a polar solvent preferably a water / ethanol mixture
• the precursor polymer solution consists of or comprises:
• a polar solvent preferably dimethyl sulfoxide (DMSO)
• DMSO dimethyl sulfoxide
• the precursor polymer solution consists of or comprises:
• PEGDA polyethylene glycol diacrylate
• a polar solvent preferably dimethylsulfoxide (DMSO)
• the precursor polymer solution consists of or comprises:
• protoporphyrin dimethyl ester or protoporphyrin disodium salt - 0.7 g of polyethylene glycol diacrylate (PEGDA)
• a polar solvent preferably dimethylsulfoxide (DMSO)
• the method of the invention comprises a step of bringing the precursor polymer solution obtained in (a) into contact with a support, resulting in the impregnation of said support with said precursor polymer solution (step noted (b)).
• step (b) is implemented at a temperature of more than 0 ° C to 50 ° C, preferably from 5 ° C to 30 ° C, more preferably at a temperature approximately equal to 20 ° C.
• step (b) is carried out at atmospheric pressure.
• the support can be any support known to a person skilled in the art, including natural or synthetic supports.
• the support can be hard or flexible.
• the support is capable of reacting with at least one radical polymerizable function of a monomer as defined above.
• the support comprises or consists of a cellulosic compound such as, for example, cotton or paper.
• the support comprises or consists of at least one synthetic or natural polymer.
• the support is made of polymer or comprises a polymer, preferably chosen from polystyrenes, polyacrylates, polymethacrylates, polyolefins (such as polyethylene, polypropylene, polybutadiene), polyurethanes, polyacrylamides, polyacrylonitriles, polyamides, polyesters, polyethers, polycarbonates, polyimides, polyketones, polysiloxanes, polyepoxides, and their copolymers and / or their mixtures.
• the natural polymer is chosen from cellulose and rubber (i.e. poly (isoprene)).
• the polymer precursor solution as defined above is applied to the support by any technique known to those skilled in the art including spray (or spraying), soaking, sizing, inkjet printing such as “dip coating” or “drop coating” (coating by drip deposition on the surface of the support).
• step (b) further comprises a drying step.
• step (b) further comprises a washing step.
• step (b) further comprises a step of evaporating the solvent.
• step (b) is implemented in a dark environment, that is to say in an environment protected from light.
• the method of the invention further comprises a step of irradiating the support impregnated with the polymer precursor solution, obtained in step (b).
• the irradiation in step (c) is irradiation by ultraviolet radiation (UV).
• the irradiation, preferably UV is carried out at an absorption wavelength less than the maximum maximum absorption wavelength of the monomer A as described above.
• the irradiation of step (c) is implemented by a UV lamp known by a person skilled in the art, preferably by a UV lamp emitting at a wavelength of about 365 nm.
• the irradiation time of step (c) is more than 0 seconds to 24 hours, preferably from ls to 12h, more preferably from ls to 3600s. According to one embodiment, the irradiation time of step (c) is more than 0 s to 24 h, preferably l s to 12 h, more preferably l s to 3600 s. According to one embodiment, the irradiation time of step (c) is comprised from ls to 60s, preferably from ls to 50s, from ls to 40s, from ls to 30s, from ls to 20s or from ls to 10s.
• the wavelength of the irradiation of step (c) is from 10 nm to 380 nm, preferably from 120 nm to 370 nm, more preferably from 200 nm to 380 nm. According to one embodiment, the wavelength of the irradiation of step (c) is approximately equal to 365 nm. According to one embodiment, the wavelength of the irradiation of step (c) is from 10 nm to 380 nm, preferably from 120 nm to 370 nm, more preferably from 200 nm to 370 nm.
• the absorption wavelength is less than the maximum absorption wavelength lhiac of the monomer A as defined above, preferably is less than 400 nm, more preferably is less than 390 nm, 380nm, or 370 nm.
• the method of the invention further comprises a step of activating the monomer A.
• the activation of the monomer A is implemented by the irradiation of the monomer A , preferably the monomer A having been incorporated into the polymer impregnating the modified support after the implementation of steps (a) to (c) of the process of the invention.
• the activation of the monomer A is implemented by light irradiation, preferably at a wavelength in the visible range, more preferably at the maximum absorption wavelength lhiac porphyrin, more preferably at about 400 nm.
• the activation of the monomer A is implemented for a period of 30 s to 24 h, preferably from 1 min to 12 h, preferably from 2 min to 6 h. According to one embodiment, the activation of the monomer A is implemented for a duration of approximately 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 1 hour, 12 hours, 1 pm, 2 pm 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h or 24h.
• the activation of the monomer A is implemented for a duration of approximately lmn, 2mn, 3mn, 4mn, 5mn, 6mn, 7mn, 8mn, 9mn, lOmn, l lmn, 12mn, 13mn, 14mn , 15mn, 16mn, 17mn, 18mn, 19mn, 20mn, 21mn, 22mn, 23mn, 24mn, 25mn, 26mn, 27mn, 28mn, 29mn, 30mn, 3 lmn, 32mn, 33mn, 34mn, 35mn, 36mn, 37mn, 38mn 39mn, 40mn, 41mn, 42mn, 43mn, 44mn, 45mn, 46mn, 47mn, 48mn, 49mn, 50mn, 5 lmn, 52mn, 53mn, 54mn, 55mn, 56mn,
• the present invention also relates to a precursor solution of a biocidal, bactericidal and / or bacteriostatic polymer, said solution being defined as described above.
• the present invention also relates to a biocidal, bactericidal and / or bacteriostatic material.
• the material of the invention is capable of being obtained by the method of the invention, as described above.
• the material of the invention comprises or consists of a support and a polymer coating, preferably said polymer coating having been obtained from a precursor polymer solution as described above.
• the support can be any support known to a person skilled in the art, including natural or synthetic supports.
• the support can be hard or flexible.
• the support is capable of reacting with at least one radical polymerizable function of a monomer as defined above.
• the support comprises or consists of a cellulosic compound such as, for example, cotton or paper.
• the support is made of polymer or comprises a polymer, preferably chosen from polystyrenes, polyacrylates, polymethacrylates, polyolefins (such as polyethylene, polypropylene, polybutadiene), polyurethanes, polyacrylamides, polyacrylonitriles, polyamides, polyesters, polyethers, polycarbonates, polyimides, polyketones, polysiloxanes, polyepoxides, and their copolymers and / or mixtures thereof.
• the coating is organic, preferably comprises or consists of an organic polymer, more preferably a polymer obtained by radical polymerization, more preferably by radical polymerization from the precursor polymer solution as previously described.
• the coating comprises or consists of one or more macromolecular chains, preferably organic macromolecular chains, more preferably organic macromolecular chains comprising one or more quaternary ammonium functions and / or more copper ions of degree d 'oxidation +11.
• the material or the coating of the invention has a biocidal, bactericidal and / or bacteriostatic activity against Gram positive (Gram +) and / or Gram negative (Gram - type bacteria). ), preferably against Escherichia coli (Gram -), Bacillus thuringiensis (Gram +) in vegetative form (bacterial form), Yersinia pestis (Gram -) and / or Bacillus anthracis (Gram +) vegetative, as well as form sporulate of B. thuringiensis. Indeed, certain bacterial species like B. thuringiensis are capable of sporulating.
• bacterial spores means a multilayer microbial form extremely resistant to environmental disturbances (nutritive stress, desiccation, heat, radiation, antibiotics, antiseptics and standard disinfectants, etc.). This resistance is notably linked to their unique structure which is particularly compact and not very permeable.
• the invention also relates to the use of the polymer precursor solution, of the material or of the process of the invention, as described above.
• the polymer precursor solution, the material or the method of the invention are useful in the field of textiles or protective coatings, or in the sanitary field.
• the polymer precursor solution, the material or the method of the invention are useful for the preparation of protective clothing or protective coatings.
• the polymer precursor solution of the invention or the biocidal, bactericidal and / or bacteriostatic material of the invention is useful for the sterilization and / or decontamination of a surface.
• the invention also relates to a kit for implementing the method of the invention.
• the kit comprises at least one compartment comprising the polymer precursor solution as described above.
• the kit comprises:
• a second compartment comprising the photoinitiator.
• the kit comprises:
• the kit is opaque and does not allow light to pass through.
• PBS Phosphate Buffered Saline
• PEGDA polyethylene glycol diacrylate
• UV ultraviolet
• ink D comprising copper but no ammonium
• ink E comprising ammonium but no copper.
• Example 2 Process for the preparation of a biocidal, bactericidal and / or bacteriostatic material
• the support was impregnated with the ink by any of the following techniques: spray, soaking, sizing, inkjet printing, “dip coating” or “drop coating” (coating by drip deposit on the surface of the support).
• the supports impregnated with the ink were then irradiated under UV at a wavelength of around 365 nm (UVKURE 120 LED lamp - 365 nm, 1.5 kW, 12W / cm 2 , Kelenn Technology, Lrance ). Both sides of the support can be irradiated.
• the irradiation time of each face of the support is between 2 s to 1 min.
• the materials grafted with the inks are, before grafting, washed with water, then washed with ethanol then autoclaved (130 ° C. for 20 min) before to perform microbiology tests.
• microbiological tests were also carried out on autoclaved materials after grafting. 2 1: Protocols for carrying out microbiology tests
• microbiological tests were carried out using the following bacterial strains:
• the protocol applied to the vegetative cells consists in the implementation of the following steps:
• the aim is to obtain an initial culture which corresponds to a bacterial culture in the exponential phase at 10 6 CFU (Colony Forming Unit) / ml which is used for the contamination of the materials to be tested.
• Example: DO 0.4 with E. coli.
• another test protocol consists in subjecting the petri dishes containing the discs to natural light for 30 seconds in a room where the temperature is regulated at 22 ° C.
• the discs are placed in sterile petri dishes with a tissue soaked in water (humid atmosphere).
• One of the boxes is exposed to light, the other is put in the dark (covered with aluminum foil).
• the exposure to light is carried out, for the exposure time of 30 seconds, by subjecting the Petri dishes containing the disks to natural light for 30 seconds in a room where the temperature is regulated; for exposure times of 24h, lh, 30 min or 5 min by incubation at 30 ° C in an incubator with the lighting system with standard LED 4000K (Lexman Light 230 V, E14, 470 Lumen).
• PBS Phosphate Buffered Saline
• the spore solutions are produced and stored in distilled water. Their stability is evaluated every month using a limit dilution count. The concentration of spores used in these tests is 10 5 CLU / mL.
• the discs are placed in sterile petri dishes with a tissue soaked in water (humid atmosphere).
• the inoculum volume for contamination is 30pL.
• One of the boxes is exposed to light, the other is in the dark (covered with aluminum foil). Spores are exposed to transplanted discs for 24 hours.
• the extraction of the spores from the samples is carried out according to a protocol similar to that applied to the vegetative cells, except the use of distilled water in place of PBS and the addition of a 30 second sonication step. before incubation for 30 minutes with shaking.
• the enumeration protocol is identical to that of vegetative cells, except for the use of distilled water in place of PBS.
• the results indicate that the inks B and C have a total bactericidal activity from 30 seconds of contact, whether in light or in the dark on Gram + bacteria (B. thuringiensis) and Gram- (E. coli).
• BSL3 laboratory tests demonstrate the bactericidal activity of ink C on the agents B. anthracis and Y. pestis in 5 min. In addition, this activity is not altered after an autoclaving cycle (130 ° C for 20 min) of the treated discs.
• Table 4 Results of the bacterial tests carried out using materials obtained with autoclaved inks B and C after grafting.
• Table 5 Tests relating to the sporicidal activity of the materials obtained with inks B and C.
• the ink C was broken down and each component was grafted separately.
• model bacterium chosen for this test was a Gram + bacterium, B. thuringiensis.
• Table 6 Bactericidal effect in the light and in the dark of materials impregnated with one of the inks A, C, D or E.
• Table 7 Sporicidal effect in the light and in the dark of materials impregnated with one of the inks A, C, D or E.
• Table 8 Bactericidal effect in the light and in the dark of materials impregnated with ink F.

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• 2018
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